Phosphoric ester preparations with reduced hygroscopicity

ABSTRACT

The present invention relates to phosphoric ester preparations with reduced hygroscopicity, to use of these as flame retardants and hydraulic fluids, and to polyurethanes which comprise the phosphoric ester preparations of the invention.

The present invention relates to phosphoric ester preparations with reduced hygroscopicity, to a method for production thereof and to use of these as flame retardants and hydraulic fluids, and also to polyurethanes which comprise the phosphoric ester preparations of the invention.

DESCRIPTION OF THE PRIOR ART

Poly(alkylene phosphates) can be used in various technical applications, for example as lubricants (cf. U.S. Pat. No. 2,632,767), hydraulic fluids (cf. U.S. Pat. No. 4,056,480), plasticizers (cf. U.S. Pat. No. 2,782,128) and as flame retardants (cf. EP 1 746 129 B1, and the European Patent Application No. 12177287.5 which is not a prior publication).

However, a problematic factor in those applications is that the poly(alkylene phosphates) are distinctly hygroscopic, see Example M-CE1. Hygroscopicity is the term used for the property that causes a substance to absorb water from the water vapour present in air. This process causes an uncontrolled rise in the water content of the poly(alkylene phosphates), and this can lead to difficulties in the applications mentioned: the increased water content in hydraulic fluids can lead to the formation of vapour bubbles which can cause undesired compressibility. Flame retardants with undesired water content can cause hydrolysis of the matrix that is to be protected (for example a plastic). In the case of production of polyurethanes, water content in the flame retardants used is always undesired, since it leads to uncontrolled foaming. Even in the case of water-blown polyurethane foams, all of the raw materials should have minimal and constant water content, in order that the properties of the foam can be adjusted in a controlled manner via the exact quantity added of water as blowing agent. In general terms, increased water content can promote the corrosion of metallic materials.

For these reasons, the use of poly(alkylene phosphates) coupled with protective measures which must prevent contact of the product with humid air along the entire product pathway. By way of example, storage tanks have to be blanketed with inert gas. This increases technical cost.

WO 2001/018088 A1 describes mixtures of oligomeric poly(alkylene phosphates) and non-oligomeric, non-halogenated organophosphorus flame retardants. However, WO 2001/018088 A1 does not address the hygroscopicity problem. WO 2001/018088 A1 gives particular preference to mixtures based on what is known as poly(ethyl ethyleneoxy) phosphate, EtO-[P(═O)OEt-CH₂CH₂—]_(n)—P(═O)(OEt)₂, where the average value of the number of the repeating units n is from 2 to 20. Poly(ethyl ethyleneoxy)phosphate is marketed by way of example as Fyrol® PNX by ICL-IP. These mixtures based on poly(ethyl ethyleneoxy)phosphate are described in WO 2001/018088 A1 as flame retardants for polyurethane foams, but feature a considerable disadvantage: that they although they can be successfully processed with polyether polyols they cannot be successfully processed with polyester polyols (see Examples).

It was therefore an object of the present invention to provide products which are based on poly(alkylene phosphates) and which feature reduced hygroscopicity, and which have good processability in polyester polyols.

The said object is achieved via mixtures which comprise certain phosphoric esters alongside an oligomer mixture of poly(alkylene phosphates).

SUMMARY OF THE INVENTION

The present invention therefore provides phosphoric ester preparations characterized in that they comprise

-   -   an oligomer mixture a) comprising at least three poly(alkylene         phosphates) corresponding to the formula (I)

-   -   -   in which

    -   R¹, R², R³ and R⁴ are respectively mutually independently a         straight-chain or branched C₁- to C₈-alkyl moiety or a         straight-chain or branched C₁- to C₄-alkoxyethyl moiety,

    -   A is a straight-chain, branched and/or cyclic C₄- to         C₂₀-alkylene moiety, or

    -   A is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the         formula —CH₂—C≡C—CH₂—, a moiety of the formula         —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, a moiety of the formula         —CHR⁵—CHR⁶—S(O)_(b)—CHR⁷—CHR⁸— or a moiety of the formula         —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—,         -   in which         -   a is an integer from 1 to 5,         -   b is an integer from 0 to 2,         -   c and d are mutually independently an integer from 1 to 5,

    -   R⁵, R⁶, R⁷ and R⁸ are mutually independently H or methyl,

R⁹ is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C—CH₂—, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II)

-   -   -   a moiety of the formula (III)

-   -   -   a moiety of the formula (IV)

-   -   -   or a moiety of the formula —C(═O)—R¹²—C(═O)—,         -   where         -   R¹⁰ and R¹¹ are respectively mutually independently H or C₁-             to C₄-alkyl or R¹⁰ and R¹¹ together are an optionally             alkyl-substituted ring having from 4 to 8 C atoms,         -   R¹² is a straight-chain, branched and/or cyclic to             C₈-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene             moiety, or a 1,4-phenylene moiety, and         -   n is an integer from 0 to 100,

    -   with the proviso that the at least three poly(alkylene         polyphosphates) of the formula (I) differ from one another at         least in the number n of the repeating units, and

    -   the average value of the number of the repeating units n of the         at least three poly(alkylene phosphates) of the formula (I) is         greater than 1.10 and smaller than 2.00,         -   and

    -   at least one phosphoric ester b) with solubility of less than         3.0 g/l in water at 25° C.

DETAILED DESCRIPTION OF THE INVENTION

Preference is given to poly(alkylene phosphates) of the formula (I) in which R¹, R², R³ and R⁴ are identical and are either ethyl, n-propyl, isopropyl, n-butyl, isobutyl or n-butoxyethyl. It is preferable that A in formula (I) is a straight-chain C₄- to C₆-alkylene moiety.

Preference is further given to poly(alkylene phosphates) of the formula (I) in which A is a moiety of the formula (II), in which R¹⁰ and R¹¹ are identical and are methyl, or is a moiety of the formulae (V), (VI) or (VII),

Preference is likewise given to poly(alkylene phosphates) of the formula (I) in which A is a moiety of the formula —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, in which a is a number from 1 to 2 and R⁵, R⁶, R⁷ and R⁸ are identical and are H or is a moiety of the formula —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—, in which c and d are mutually independently an integer from 1 to 2, and R⁹ is a moiety of the formula (II), where R¹⁰ and R¹¹ are identical and are methyl.

Preference is given to phosphoric ester preparations of the invention which comprise an oligomer mixture a) comprising at least three poly(alkylene phosphates) of the formula (I),

-   -   in which     -   R¹, R², R³ and R⁴ are respectively mutually independently a         straight-chain or branched C₁- to C₄-alkyl moiety or a C₁- or         C₂-alkoxyethyl moiety,     -   A is a straight-chain or branched C₄- to C₁₀-alkylene moiety, or     -   A is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the         formula —CH₂—C≡C—CH₂—, a moiety of the formula         —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, a moiety of the formula         —CHR⁵—CHR⁶—S(O)_(b)—CHR⁷—CHR⁸— or a moiety of the formula         —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—,         -   in which         -   a is an integer from 1 to 5,         -   b is an integer from 0 to 2,         -   c and d are mutually independently an integer from 1 to 5,         -   R⁵, R⁶, R⁷ and R⁸ are mutually independently H or methyl,         -   R⁹ is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of             the formula —CH₂—C≡C—CH₂—, a 1,2-phenylene moiety, a             1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of             the formula (II)

-   -   -   a moiety of the formula (III)

-   -   -   a moiety of the formula (IV)

-   -   -   or a moiety of the formula —C(═O)—R¹²—C(═O)—,         -   where         -   R¹⁰ and R¹¹ are respectively mutually independently H or C₁-             or C₂-alkyl,         -   R¹² is a straight-chain or branched C₂- to C₆-alkylene             moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a             1,4-phenylene moiety, and         -   n is an integer from 0 to 100.

Very particular preference is given to phosphoric ester preparations of the invention which comprise an oligomer mixture a) comprising at least three poly(alkylene phosphates) of the formula (I)

-   -   in which     -   R¹, R², R³ and R⁴ are respectively mutually independently a         straight-chain or branched C₁- to C₄-alkyl moiety or an         n-butoxyethyl moiety,     -   A is a straight-chain C₄- to C₆-alkylene moiety, or     -   A is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the         formula —CH₂—C≡C—CH₂—, a moiety of the formula         —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, a moiety of the formula         —CHR⁵—CHR⁶—S(O)_(b)—CHR⁷—CHR⁸— or a moiety of the formula         —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—,         -   in which         -   a is an integer from 1 to 5,         -   b is an integer from 0 to 2,         -   c and d are mutually independently an integer from 1 to 5,         -   R⁵, R⁶, R⁷ and R⁸ are mutually independently H or methyl,     -   R⁹ is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the         formula —CH₂—C≡C—CH₂—, a 1,2-phenylene moiety, a 1,3-phenylene         moiety, a 1,4-phenylene moiety, or a moiety of the formula (II)

-   -   -   a moiety of the formula (III)

-   -   -   a moiety of the formula (IV)

-   -   -   or a moiety of the formula —C(═O)—R¹²—C(═O)—,         -   where         -   R¹⁰ and R¹¹ are respectively mutually independently H or C₁-             or C₂-alkyl,         -   R¹² is a straight-chain or branched C₂- to C₆-alkylene             moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a             1,4-phenylene moiety, and         -   n is an integer from 0 to 100.

Preference is in particular given to phosphoric ester preparations of the invention which comprise an oligomer mixture a) comprising at least three poly(alkylene phosphates) of the formula (I)

-   -   in which     -   R¹, R², R³ and R⁴ are identical and are ethyl, n-propyl,         isopropyl, n-butyl, isohutyl or n-butoxyethyl,     -   A is a straight-chain C₄- to C₆-alkylene moiety, or     -   A is a moiety of the formulae

-   -   or     -   A is a moiety —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, in which a is an         integer from 1 to 2 and R⁵, R⁶, R⁷ and R⁸ are identical and are         H, or is a moiety —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—, in         which c and d are mutually independently an integer from 1 to 2,         R⁵, R⁶, R⁷ and R⁸ are identical and are H, R⁹ is a moiety of the         formula (II), where R¹⁰ and R¹¹ are identical and are methyl,     -   and     -   n is an integer from 0 to 20.

It is preferable that the oligomer mixtures a) present in the phosphoric ester preparations of the invention and the poly(alkylene phosphates) present therein are halogen-free. For the purposes of the present invention, the expression “halogen-free” means that the poly(alkylene phosphates) of the formula (I) do not comprise the elements fluorine, chlorine, bromine and/or iodine and that the oligomer mixtures a) present in the phosphoric ester preparations of the invention do not comprise any other substances in a quantity that causes content of one or more of the elements fluorine, chlorine, bromine and iodine to be greater than 5000 ppm, based on the oligomer mixture a).

The oligomer mixtures a) present in the phosphoric ester preparations of the invention comprise at least three, preferably more than three different poly(alkylene phosphates) of the general formula (I) which differ from one another at least in the number n of the repeating units and thus in their molar mass. The person skilled in the art uses suitable average values to describe oligomer mixtures of this type, for example the number-average molar mass M_(n) and the average value of the number of the repeating units n in the molecules of the formula (I) present in the oligomer mixture.

The number-average molar mass M_(n) of the poly(alkylene phosphates) of the formula (I) present in the oligomer mixture a) in the invention is determined via gel permeation chromatography with tetrahydrofuran as eluent against polystyrene standards. This method is known to the person skilled in the art, for example from DIN 55672-1:2007-08. From M_(n) it is easily possible, by considering the stoichiometry of the formula (I), to calculate the average value of the number of the repeating units n in the poly(alkylene phosphates) present in the oligomer mixture a) (see Production Example).

The phosphoric esters b) present in the phosphoric ester preparations of the invention are preferably esters of orthophosphoric acid having identically or differently substituted alkyl, alkylene, alkoxyalkylene, arylalkyl, aryl, arylene or hetaryl moieties. The materials can also be mixtures of various esters of the sort frequently encountered in technical products of this type.

It is preferable that the phosphoric esters b) are compounds of the formula (VIII)

-   -   in which     -   R¹³, R¹⁴, R¹⁵ and R¹⁶ are respectively mutually independently         straight-chain or branched C₄- to C₁₂-alkyl, C₄- to         C₁₂-alkoxyalkyl, C₃- to C₁₂-chloroalkyl, C₃- to         C₁₂-dichloroalkyl or optionally mono- or poly-C₁- to         C₄-alkyl-substituted C₆- to C₁₀-aryl,     -   X is a C₄- to C₈-alkylene moiety, a 1,2-phenylene moiety, a         1,3-phenylene moiety, a 1,4-phenylene moiety or a moiety of the         formula (II),

-   -   in which     -   R¹⁰ and R¹¹ are as defined above,     -   and     -   m is 0 or 1.

It is particularly preferable that the phosphoric esters b) are compounds of the formula (VIII)

-   -   in which     -   R¹³, R¹⁴, R¹⁵ and R¹⁶ are mutually independently optionally         mono- or poly-C₁- to C₄-alkyl-substituted phenyl,     -   X is a C₄- to C₈-alkylene moiety, a 1,2-phenylene moiety, a         1,3-phenylene moiety, a 1,4-phenylene moiety or a moiety of the         formula (II),

-   -   in which R¹⁰ and R¹¹ are as defined above,     -   and m is 0 or 1.

Examples of the preferred phosphoric esters b) are triphenyl phosphate, diphenyl cresyl phosphate, tricresyl phosphate, isopropylated or butylated aryl phosphates, bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), hydroquinone bis(diphenyl phosphate), neopentyl glycol bis(diphenyl phosphate), triisobutyl phosphate, tributoxyethyl phosphate, tris(chloroisopropyl)phosphate and tris(dichloropropyl)phosphate and mixtures of these.

The phosphoric esters b) are commercially obtainable products or can be produced by a known method. It is also possible to use technical products as phosphoric esters b). It is preferable here to use those technical products which are termed “neutral” phosphoric esters, i,e. which have an acid number below 10 mg KOH/g, preferably below 5.0 mg KOH/g and particularly preferably below 2.0 mg KOH/g.

In principle, the oligomer mixtures a) can be produced via methods known to the person skilled in the art for the production of alkyl phosphates. By way of example, the oligomer mixtures a) can be produced via the reaction of alkyl dichlorophosphates of the formula MO—POCl₂, in which M is a moiety R¹, R², R³ or R⁴ and R¹, R², R³ and R⁴ comply with the general and preferred definitions given above, with dihydroxy compounds of the formula HO-A-OH, in which A complies with the general and preferred definitions given above, and with one or more monohydroxy compounds M-OH, in which M is defined as above, or via reaction of dihydroxy compounds of the formula HO-A-OH, in which A complies with the general and preferred definitions given above, with phosphorus oxychloride POCl₃ and with one or more monohydroxy compounds M-OH, in which M is a moiety R¹, R², R³ or R⁴, and R¹, R², R³ and R⁴ comply with the general and preferred definitions given above, or via reaction of one or more trialkyl phosphates (MO)₃PO, in which M is as defined above, with phosphorus pentoxide P₂O₅ and with a cyclic ether.

Preference is given in the invention to the production process via reaction of dihydroxy compounds of the formula HO-A-OH, in which A complies with the general and preferred definitions given above, with phosphorus oxychloride POCl₃ and with at least one monohydroxy compound M-OH, in which M is a moiety R¹, R², R³ or R⁴, and R¹, R², R³ and R⁴ comply with the general and preferred definitions given above.

The present invention further provides a process for the production of the phosphoric ester preparations of the invention, characterized in that an oligomer mixture a) complying with the general or preferred definition given above and at least one phosphoric ester b) complying with the general or preferred definition given above are mixed with one another.

The phosphoric ester preparation of the invention generally comprises from 30 to 70% by weight, preferably from 40 to 60% by weight, of oligomer mixture a) and from 30 to 70% by weight, preferably from 40 to 60% by weight, of at least one phosphoric ester b), based on the entire preparation.

It is preferable that the phosphoric ester preparations of the invention are liquid at about 23° C.

It is preferable that the viscosity of the phosphoric ester preparations of the invention is from 20 to 5000 mPas at 23° C. It is particularly preferable that the viscosity is from 20 to 1000 mPas at 23° C.

The phosphoric ester preparations of the invention can preferably comprise, alongside components a) and b), as required by application sector, one or more auxiliaries, for example from the group of the solvents, antioxidants, stabilizers and colorants. Examples of these auxiliaries that can be used are:

-   -   solvents such as alkyl esters of aliphatic or aromatic di- or         tricarboxylic acids,     -   antioxidants and stabilizers such as sterically hindered         trialkylphenols, alkyl esters of         3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,         benzofuran-2-ones, secondary aromatic amines, phosphites,         phenothiazines or tocopherols, and     -   dyes such as soluble organic colorants, iron oxide pigments or         carbon blacks.

The phosphoric ester preparations of the invention are suitable for use as flame retardants and for the production of flame retardant preparations. The present invention further provides the use of the phosphoric ester preparations of the invention as flame retardants.

The phosphoric esters preparations can be used as flame retardants in any of the applications known to the person skilled in the art for flame retardants. It is preferable that the phosphoric ester preparation of the invention is used as flame retardant for

-   -   synthetic polymers such as polyolefins, polyvinyl chloride,         polycarbonates, styrene-based (co)polymers, polyamides,         polyesters, polyurethanes, and thermosets such as epoxy resins,         unsaturated polyester resins and phenol-formaldehyde resins,     -   plant-derived materials, such as wood, wood-plastic composites,         paper and paperboard, and     -   animal-derived materials such as leather.

It is particularly preferable that the phosphoric ester preparations of the invention are used as flame retardants for polyurethanes. It is very particularly preferable that the phosphoric ester preparations are used as flame retardants for polyurethane foams.

The polyurethane foams are flexible polyurethane foams or rigid polyurethane foams. It is preferable that the phosphoric ester preparations are used as flame retardants for flexible polyurethane foams which are produced from polyether polyols, i.e. flexible polyether-polyurethane foams. In an alternative, likewise preferred, embodiment of the invention the phosphoric ester preparations are used as flame retardants for flexible polyurethane foams which are produced from polyester polyols, i.e. flexible polyester-polyurethane foams.

The present invention further provides polyurethanes which comprise at least one phosphoric ester preparation of the invention. These polyurethanes can be produced in flame-retardant form via suitable selection of the quantity of phosphoric ester preparations present.

The flame-retardant polyurethanes of the invention can be produced by reacting organic polyisocyanates with compounds having at least two hydrogen atoms reactive towards isocyanates with conventional blowing agents, stabilizers, activators and/or other conventional auxiliaries and additives in the presence of at least one phosphoric ester preparation of the invention.

The quantity used of the phosphoric ester preparations of the invention is from 0.5 to 30 parts by weight, preferably from 3 to 25 parts by weight, based on 100 parts by weight polyol component.

The polyurethanes are isocyanate-based polymers which mainly have urethane groups and/or isocyanurate groups and/or allophanate groups and/or uretdione groups and/or urea groups and/or carbodiimide groups. The production of isocyanate-based polymers is known per se and is described by way of example in German Offenlegungschrift 16 94 142, 16 94 215 and 17 20 768, and also in Kunststoff-Handbuch [Plastics handbook] Volume VII, Polyurethane [Polyurethanes], edited by G. Oertel, Carl-Hanser-Verlag Munich, Vienna 1993.

The flame-retardant polyurethanes of the invention are thermoset polyurethanes, polyurethane foams, polyurethane elastomers, thermoplastic polyurethanes, polyurethane coatings and polyurethane lacquers, polyurethane adhesives and polyurethane binders or polyurethane fibres.

In one preferred embodiment of the invention, the flame-retardant polyurethanes of the invention are flame-retardant polyurethane foams.

Polyurethane foams are broadly divided into flexible and rigid foams. Although flexible and rigid foams can in principle have approximately the same envelope density and the same composition, flexible polyurethane foams have only little crosslinking and exhibit only low resistance to deformation under pressure. In contrast to this, the structure of rigid polyurethane foams is composed of highly crosslinked units and rigid polyurethane foam exhibits very high resistance to deformation under pressure. Typical rigid polyurethane foam has closed cells and has low thermal conductivity. Primary factors influencing the subsequent foam structure and foam properties during the production of polyurethanes via reaction of polyols with isocyanates are the structure and molar mass of the polyol, and the reactivity and number (functionality) of hydroxy groups present in the polyol. Further details concerning rigid and flexible foams, the starting materials that can be used to produce these, and also processes for producing the same, are found in Norbert Adam, Geza Avar, Herbert Blankenheim, Wolfgang Friederichs, Manfred Giersig, Eckehard Weigand, Michael Halfmann, Friedrich-Wilhelm Wittbecker, Donald-Richard Larimer, Udo Maier, Sven Meyer-Ahrens, Karl-Ludwig Noble and Hans-Georg Wussow: “Polyurethanes”, Ullmann's Encyclopedia of Industrial Chemistry Release 2005, Electronic Release, 7th Edn., Chapter 7 (“Foams”), Wiley-VCH, Weinheim 2005.

Preferred envelope densities of the polyurethane foams of the invention are from 10 to 150 kg/m³. They particularly preferably have envelope densities of from 20 to 50 kg/m³.

Starting components used for the production of the isocyanate-based foams are as follows:

1) Aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates (e.g. W. Siefken in Justus Liebigs Annalen der Chemie, 562, pp. 75-136), for example those of the formula Q(NCO)_(n), in which n=from 2 to 4, preferably from 2 to 3, and Q is an aliphatic hydrocarbon moiety having from 2 to 18, preferably from 6 to 10, C atoms, a cycloaliphatic hydrocarbon moiety having from 4 to 15, preferably from 5 to 10, C atoms, an aromatic hydrocarbon moiety having from 6 to 15, preferably from 6 to 13, C atoms or an araliphatic hydrocarbon moiety having from 8 to 15, preferably from 8 to 13, C atoms. Particular preference is generally given to the polyisocyanates that derive from tolylene 2,4- and/or 2,6-diisocyanate or from diphenylmethane 4,4′- and/or 2,4′-diisocyanate, these being readily obtainable in industry.

2) Compounds having at least two hydrogen atoms reactive towards isocyanates with molar mass from 400 to 8000 g/mol (“polyol component”). These are not only compounds having amino groups, thiol groups or carboxy groups but also preferably compounds having hydroxy groups, in particular compounds having from 2 to 8 hydroxy groups. If the polyurethane foam is to he a flexible foam, it is preferable to use polyols with molar masses from 2000 to 8000 g/mol and from 2 to 6 hydroxy groups per molecule. If, in contrast, the intention is to produce a rigid foam it is preferable to use highly branched polyols with molar masses from 400 to 1000 g/mol and from 2 to 8 hydroxy groups per molecule. The polyols are polyethers and polyesters, and also polycarbonates and polyesteramides, these being known per se for the production of homogeneous and of cellular polyurethanes, being described for example in German Offenlegungschrift 28 32 253. Preference is given in the invention to the polyesters and polyethers having at least two hydroxy groups.

The polyurethane foams of the invention can therefore be produced in the form of rigid or flexible foams via appropriate selection, easily found in the prior art, of the starting materials.

Other optional starting components are compounds having at least two hydrogen atoms reactive towards isocyanates and molar mass from 32 to 399 g/mol. Again here these are compounds having hydroxy groups and/or amino groups and/or thiol groups and/or carboxy groups, preferably compounds having hydroxy groups and/or amino groups, where said compounds serve as chain extenders or crosslinking agents. These compounds generally have from 2 to 8, preferably from 2 to 4 hydrogen atoms reactive towards isocyanates. Examples of these are likewise described in German Offenlegungschrift 28 32 253.

3) Water and/or volatile organic substances as blowing agent, e.g. n-pentane, isopentane, cyclopentane, acetone, halogenated alkanes, such as trichloromethane, methylene chloride or chlorofluoroalkanes, CO₂ and others.

4) Concomitant use is optionally made of auxiliaries and additions such as catalysts of the type known per se, surface-active additives such as emulsifiers and foam stabilizers, reaction retarders, e.g. acidic substances such as hydrochloric acid or organic acyl halides, and also cell regulators of the type known per se, for example paraffins or fatty alcohols and dimethylpolysiloxanes, and also pigments or dyes and other flame retardants, stabilizers to counter effects of ageing and of weathering, core-discoloration inhibitors, plasticizers and fungistatic and bacteriostatic substances, and also fillers such as barium sulphate, kieselguhr, carbon black or purified chalk (German Offenlegungschrift 27 32 292). Particular core-discoloration inhibitors that can be present are sterically hindered trialkylphenols, alkyl esters of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, benzofuran-2-ones, secondary aromatic amines, phosphites, phenothiazines or tocopherols.

The following compounds can also be present as further flame retardants alongside the phosphoric ester preparations of the invention in the polyurethanes of the invention:

-   -   organic phosphorus compounds such as triethyl phosphate,         triphenyl phosphate, diphenyl cresyl phosphate, tricresyl         phosphate, isopropylated or butylated aryl phosphates, aromatic         bisphosphates, neopentyl glycol bis(diphenyl phosphate),         chlorinated phosphoric esters such as         tris(chloroisopropyl)phosphate or tris(dichloropropyl)phosphate,         dimethyl methanephosphonate, diethyl ethanephosphonate, dimethyl         propanephosphonate, diethylphosphinic acid derivatives and salts         of diethylphosphinic acid, other oligomeric phosphates or         phosphonates, hydroxylated phosphorus compounds,         5,5-dimethyl-1,3,2-dioxaphosphorinane 2-oxide derivatives,         9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) and         its derivatives,     -   inorganic phosphorus compounds such as ammonium phosphate,         ammonium polyphosphate, melamine phosphate, melamine         polyphosphate,     -   nitrogen compounds such as melamine, melamine cyanurate,     -   bromine compounds such as alkyl esters of a tetrabromobenzoic         acid, brominated dials produced from tetrabromophthalic         anhydride, brominated polyols, brominated diphenyl ethers,     -   inorganic flame retardants such as aluminium hydroxide,         boehmite, magnesium hydroxide, expanded graphite or clay         minerals.

Other examples of surface-active additives and foam stabilizers that can optionally be used concomitantly in the invention, and also of cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, colorants and fillers, and also fungistatic and bacteriostatic substances are described in Kunststoff-Handbuch [Plastics Handbook], Volume VII, Carl-Hanser-Verlag, Munich, 1993, pp. 104 to 123, as also are details concerning the mode of use and of action of these additives,

The present invention further provides a process for the production of polyurethanes via reaction of organic polyisocyanates with compounds having at least two hydrogen atoms reactive towards isocyanates and conventional blowing agents, stabilizers, catalysts, activators and/or other conventional auxiliaries and additives at from 20 to 80° C., by using a quantity of from 0.5 to 30 parts by weight, based on 100 parts by weight of polyol component, of at least one phosphoric ester preparation of the invention. It is preferable that the quantity used of the phosphoric ester preparations is from 3 to 25 parts by weight, based on 100 parts by weight of polyol component.

The process for the production of polyurethanes of the invention is carried out by reacting the reaction components described above in the single-stage process known per se, in the prepolymer process or in the semiprepolymer process, often with use of machinery such as that described in U.S. Pat. No. 2,764,565. Details concerning processing equipment which can also be used in the invention are described in Kunststoff-Handbuch [Plastics Handbook] Volume VII, Polyurethane [Polyurethanes], edited by G. Oertel, Carl-Hanser-Verlag, Munich, Vienna 1993, pp. 139 to 192.

The process of the invention can also produce cold-curing foams (GB Patent 11 62 517, German Offenlegungschrift 21 53 086). However, it is also of course possible to produce foams via block foaming or by the twin-belt process known per se. Polyisocyanurate foams are produced by using the processes and conditions known for that purpose.

The process of the invention permits the production of polyurethane foams in the form of rigid or flexible foams continuously or batchwise, or in the form of foam mouldings. Preference is given to the process of the invention in the production of flexible foams produced via a block foaming process.

The polyurethanes obtainable in the invention are preferably used in furniture cushioning, textile inlays, mattresses, vehicle seats, armrests, components, seat cladding and dashboard cladding, cable sheathing, gaskets, coatings, lacquers, adhesives, adhesion promoters and fibres.

The present invention provides the use of the phosphoric ester preparations of the invention as hydraulic fluids or for the production of hydraulic fluids. It is preferable that the phosphoric ester preparations are used in flame-retardant hydraulic fluids.

The phosphoric ester preparations of the invention can be produced from known components by known methods. The liquid phosphoric ester preparations are easy to meter and are therefore very easy to process. By virtue of the reduced hygroscopicity, there is reduced risk of undesired contamination with water.

The examples below provide further explanation of the invention, but there is no intention that the invention be restricted thereby.

EXAMPLES Production Example

Oligomer mixture a) of poly(alkylene phosphates) of the formula (I) where R¹═R²═R³═R⁴=ethyl and A=—CH₂CH₂OCH₂CH₂—

306.7 parts by weight of phosphorus oxychloride were charged to a reactor with stirrer, dropping funnel, reflux condenser and vacuum equipment. The temperature of the phosphorus oxychloride was controlled to from 10 to 20° C. A vacuum of from 500 to 700 mbar was applied and 118.7 parts by weight of diethylene glycol were added dropwise. Once the dropwise addition had ended, the pressure was lowered further to a final value of from 5 to 15 mbar and the temperature was raised to from 20 to 30° C. The residue was an almost colourless liquid.

618.2 parts by weight of ethanol were used as initial charge at from 20 to 30° C. in another reactor with stirrer, dropping funnel and reflux condenser, and the residue obtained above was admixed. Stirring of the mixture was continued at from 20 to 30° C. until the reaction ended, and the mixture was then neutralized via addition of concentrated aqueous sodium hydroxide solution. A sufficient amount of dichloromethane and water was then added to give two clear liquid phases. These were separated, and the organic phase was freed from the dichloromethane, excess ethanol and water via distillation. The residue was the oligomer mixture of the invention in the form of a colourless liquid. The viscosity of the product was determined at 23° C. by a commercially available falling-ball viscometer, and was 58 [mPas].

Determination of the Average Value of the Number of Repeating Units F in the Molecules Corresponding to the Formula (I) Present in the Oligomer Mixture A) in Accordance with Above Production Specification

Analysis via gel permeation chromatography (GPC) showed that the product produced according to the above specification was an oligomer mixture. The number-average molar mass M_(n) of the oligomer mixture was determined via GPC with tetrahydrofuran as eluent against polystyrene standards by a method based on that of DIN 55672-1:2007-08. The average value of the number of repeating units n in the poly(alkylene phosphates) corresponding to the formula (I) present in the oligomer mixture was calculated in accordance with the following formula from the number-average molar mass M_(n) measured:

n =(M _(n) −M _(E))/M _(R)

-   -   where     -   n: is the average value of the number of repeating units of the         poly(alkylene phosphates) of the formula (I) present in the         oligomer mixture,     -   M_(n): is the number-average molar mass in g/mol determined via         gel permeation chromatography,     -   M_(E): is the sum of the molar masses of the terminal groups in         g/mol and     -   M_(R): is molar mass of the repeating unit in g/mol.

For the oligomer mixtures of poly(alkylene phosphates) of the formula (I) produced, where R¹═R²═R³═R⁴=ethyl and A=—CH₂CH₂OCH₂CH₂—, the values are M_(E)=182.16 g/mol and M_(R)=194.14 g/mol. The value obtained for M_(n) was 462 and thus n=1.44.

Determination of Water Absorption

The oligomer mixture a) produced in accordance with the above specification was used for the Examples. Water absorption was determined on the pure oligomer mixture a) (Comparative Example M-CE1), and also on mixtures of 50% by weight of oligomer mixture a) and 50% by weight of phosphoric ester b) according to Table 1. All of the phosphoric esters listed in Table 1 were commercially obtainable products with acid number <0.1 mg KOH/g. For determination of water absorption, 100 ml of each mixture to be tested were charged to a 250 ml glass beaker (height 12 cm, diameter 6 cm) and placed, uncovered, for 7 days in a chamber under controlled climatic conditions at 23° C. and 50% relative humidity. The water content of the mixtures was determined by means of Karl-Fischer titration in accordance with DIN 51777. Each of the samples was homogenized by stirring before the water determination.

TABLE 1 Phosphoric esters b) used and water solubility of these Solubility in water Common name Chemical name at 25° C. [g/l] TEP Triethyl phosphate miscible TiBP Triisobutyl phosphate 0.27 TDCP Tris(2,3-dichloroisopropyl) 0.10 phosphate DPC Diphenyl cresyl phosphate 0.0026 RDP Resorcinol bis(diphenyl 0.0011 phosphate) TCPP Tris (2-chloroisopropyl) 1.08 phosphate TBPP tert-Butylated triphenyl 0.0027 phosphate TBEP Tris(2-butoxyethyl) 0.70 phosphate IPP Isopropylated triphenyl 0.00033 phosphate

TABLE 2 Water absorption after 7 days for phosphoric ester mixtures of the invention made of 50% by weight of oligomer mixture a) and 50% by weight of phosphoric ester b) (Examples M-IE1 to M-IE8) and Comparative Examples M-CE1 to M-CE2 not of the invention Water absorption after 7 days Mixture Neutral phosphoric ester [% by weight] M-CE1 — 2.30 M-CE2 TEP 3.09 M-IE1 TiBP 1.91 M-IE2 DPC 0.91 M-IE3 IPP 0.70 M-IE4 TBPP 0.87 M-IE5 RDP 0.90 M-IE6 TCPP 1.24 M-IE7 TDCP 0.87 M-IE8 TBEP 2.05

Evaluation of Water Absorption Results

According to the results listed in Table 2, the oligomer mixture a) alone (Comparative Example M-CE1) exhibits considerable water absorption under the test conditions. In the absence of complicated precautions, the product rapidly absorbs a quantity of water that can be problematic in industrial applications.

The phosphoric ester preparations M-IE1 to M-IE8 of the invention exhibit markedly lower water absorption than the oligomer mixture a) alone. They therefore feature reduced hygroscopicity, and this is an advantage in water-sensitive industrial applications.

In contrast, the mixture M-CE2, not of the invention, made of the oligomer mixture a) and of the phosphoric ester triethyl phosphate with water solubility of more than 3.0 g/l at 25° C. absorbs markedly more water than the oligomer mixture a) alone, and therefore has markedly poorer suitability for water-sensitive industrial applications.

Production of Flexible Polyurethane Foams

TABLE 3 Raw materials used for the production of flexible polyether-polyurethane foams Component Function Description A Polyol Arcol ® 1105 (Bayer MaterialScience), polyether polyol with OHN 56 mg KOH/g B Blowing agent Water C Catalyst Addocat 108 ® (Rhein Chemie), 70% solution of bis(2-dimethylaminoethyl) ether in dipropylene glycol D Catalyst Addocat ® SO (Rhein Chermie), tin(II) 2-ethylhexanoate E Stabilizer Tegostab ® B 8232 (Degussa), silicone stabilizer M Flame retardant Phosphoric ester preparations from Table 2 G Diisocyanate Desmodur ® T 80 (Bayer MaterialScience), tolylene diisocyanate, isomer mixture

Production of Flexible Polyether-Polyurethane Foams

Table 3 states the raw materials for the production of flexible polyether-polyurethane foams. The components stated in terms of type and quantity in Table 4, with the exception of the diisocyanate (component G), were mixed to give a homogeneous mixture. The diisocyanate was then added and incorporated by brief vigorous stirring. After a cream time of from 15 to 20 s and a full rise time of from 170 to 200 s, a flexible polyether-polyurethane foam was obtained with envelope density 33 kg/m³. Uniformly fine-pored foams were obtained in all of the Examples.

Determination of Flame Retardancy

The flexible polyurethane foams (polyether and polyester) were tested in accordance with the specifications of the Federal Motor Vehicle Safety Standards FMVSS 302 and allocated to the fire classes SE (self-extinguishing), SE/NBR (self-extinguishing/no burning rate), SE/BR (self-extinguishing/with burning rate), BR (burning rate) and RB (rapid-burning). The fire tests were carried out five times for each Example. The worst result from each series of five has been reported in Table 4.

TABLE 4 Composition (parts by weight) and test results for Examples IE1 to IE2 of the invention and for Comparative Examples CE0 to CE1, not of the invention, relating to flexible polyether-polyurethane foams Example CE0 CE1 IE1 IE2 A 100 100 100 100 B 3.0 3.0 3.0 3.0 C 0.08 0.08 0.08 0.08 D 0.16 0.16 0.16 0.16 E 0.80 0.80 0.80 0.80 M-CE1 6 M-IE4 6 M-IE5 6 G 40.9 40.9 40.9 40.9 MVSS class RB SE SE SE

Evaluation of Results Relating to Flexible Polyether-Polyurethane Foams

In the absence of a flame retardant (Comparative Example CEO) the flexible polyurethane foam is rapidly consumed by combustion (MVSS fire class RB). Foams with an oligomer mixture a) alone (Comparative Example CEO, and also with the phosphoric ester preparations of the invention (Inventive Examples IE1 and IE2) achieve the best MVSS fire class SE (self-extinguishing) when six parts of flame retardant are used.

Examples IE1 and IE2 show that the phosphoric ester preparations of the invention with reduced hygroscopicity exhibit the same flame-retardant effect as the known hygroscopic oligomer mixtures a) alone.

Production of Flexible Polyester-Polyurethane Foams

Table 5 states the raw materials for the production of flexible polyester-polyurethane foams. The components stated in terms of type and quantity in Table 6, with the exception of the two diisocyanates (components G and H), were mixed to give a homogeneous mixture. The two premixed diisocyanates were then added and incorporated by brief vigorous stirring. After a cream time of from 10 to 15 s and a full rise time of from 70 to 80 s, a flexible polyester-polyurethane foam was obtained with envelope density 29 kg/m³. The foam structure of the flexible polyester-polyurethane foams was dependent on the flame retardants used. It is recorded in Table 6 as “uniformly fine-pored” (“uf”) or “non-uniformly coarse-pored” (“nc”).

TABLE 5 Raw materials used for the production of flexible polyester-polyurethane foams (Inventive Examples IE6 and IE7 and Comparative Examples CE2 to CE4, not of the invention) Component Function Description A Polyol Desmophen ® 2200 B (Bayer MaterialScience), polyester polyol with OHN 60 mg KOH/g B Blowing agent Water C Catalyst Niax ® A-30 (Momentive), amine D Catalyst Addocat ® 117 (Rhein Chemie), tertiary amine E Stabilizer Tegostab ® B 8324 (Degussa), silicone stabilizer M-IE4 and Flame retardant Phosphoric ester preparations from Table 2 M-IE5 M-CE3 Flame retardant Mixture of 50% by weight of Fyrol ® PNX from ICL-IP (oligomeric phosphate esters of the formula EtO—[P(═O)OEt— CH₂CH₂—]_(n)—P(═O)(OEt)₂, CAS Reg. No. 184538-58-7, M_(n) = 640 g/mol from GCP (see above), average value of the number of repeating units n = 3.01; viscosity 1241 mPas at 23° C.) with 50% by weight of RDP G Diisocyanate Desmodur ® T 80 (Bayer MaterialScience), tolylene diisocyanate, isomer mixture H Diisocyanate Desmodur ® T 65 (Bayer MaterialScience), tolylene diisocyanate, isomer mixture

TABLE 6 Composition (parts by weight) and test results for Examples IE3 to IE4 of the invention and for Comparative Examples CE2 to CE4, not of the invention, relating to flexible polyester-polyurethane foams Example CE2 CE3 CE4 IE3 IE4 A 100 100 100 100 100 B 4.0 4.0 4.0 4.0 4.0 C 0.25 0.25 0.25 0.25 0.25 D 0.25 0.25 0.25 0.25 0.25 E 1.0 1.0 1.0 1.0 1.0 M-CE1 6 M-CE3 6 M-IE4 6 M-IE5 6 G 24.1 24.1 24.1 24.1 24.1 H 24.1 24.1 24.1 24.1 24.1 Foam structure uf uf nc uf uf MVSS class RB SE — SE SE

Evaluation of the Results Relating to Flexible Polyester-Polyurethane Foams

In the absence of a flame retardant (Comparative Example CE2) the flexible polyester-polyurethane foam features a uniformly fine-pored foam structure, but is rapidly consumed by combustion (MVSS fire class RB). Addition of 6 parts of an oligomer mixture a) alone in accordance with the production specification stated above (Comparative Example CE3) does not alter the foam structure and permits achievement of the best MVSS fire class SE (self-extinguishing). However, the high hygroscopicity of the pure oligomer mixture a) M-CE1 is disadvantageous.

A mixture described in WO 2001/018088 A1, made of an oligomer mixture of poly(alkylene phosphate) of the formula EtO-[P(═O)OEt-CH₂CH₂—]_(n)—P(═O)(OEt)₂ (M-CE3; CAS Reg. No. 184538-58-7, average value of the number of repeating units n=3.01) and RDP in a ratio by mass of 1:1 cannot be successfully processed to give a flexible polyester-polyurethane foam (Comparative Example CE4). The foam is non-uniformly coarse-pored and thus unusable. This shows that the mixture M-CE3 from the prior art is not compatible with polyester polyols.

In contrast to this, the phosphoric ester preparations of the invention (Inventive Examples IE3 and IE4) permit the production of foams with the desired, uniformly fine-pored foam structure. Inventive Example IE4 uses the phosphoric ester preparation M-IE5 of the invention which, like M-CE3, comprises 50% by weight of RDP as phosphoric ester b), and is therefore directly comparable with Comparative Example CE4. The foams from Inventive Examples IE3 and IE4 achieve the best MVSS fire class SE (self-extinguishing) with 6 parts of flame retardant.

Examples IE3 and IE4 show that the phosphoric ester preparations of the invention with reduced hygroscopicity have good processability with polyester polyols and exhibit the same flame-retardant effect as the known hygroscopic oligomer mixtures a) alone. 

What is claimed is:
 1. A phosphoric ester preparation which comprises i) an oligomer mixture a) comprising at least three poly(alkylene phosphates) corresponding to the formula (I)

in which R¹, R², R³ and R⁴ are respectively mutually independently a straight-chain or branched C₁- to C₈-alkyl moiety or a straight-chain or branched C₁- to C₄-alkoxyethyl moiety, A is a straight-chain, branched and/or cyclic C₄- to C₂₀-alkylene moiety, or A is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C—CH₂—, a moiety of the formula —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, a moiety of the formula —CHR⁵—CHR⁶—S(O)_(b)—CHR⁷—CHR⁸— or a moiety of the formula —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—, in which a is an integer from 1 to 5, b is an integer from 0 to 2, c and d are mutually independently an integer from 1 to 5, R⁵, R⁶, R⁷ and R⁸ are mutually independently H or methyl, R⁹ is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C—CH₂—, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II)

a moiety of the formula (III)

a moiety of the formula (IV)

or a moiety of the formula —C(═O)—R¹²—C(O)—, where R¹⁰ and R¹¹ are respectively mutually independently H or C₁- to C₄-alkyl or R¹⁰ and R¹¹ together are an optionally alkyl-substituted ring having from 4 to 8C atoms, R¹² is a straight-chain, branched and/or cyclic C₂- to C₈-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a 1,4-phenylene moiety, and n is an integer from 0 to 100, with the proviso that the at least three poly(alkylene phosphates) of the formula (I) differ from one another at least in the number n of the repeating units, and the average value of the number of the repeating units n of the at least three poly(alkylene phosphates) of the formula (I) is greater than L10 and smaller than 2.00, and ii) at least one phosphoric ester b) with solubility of less than 3.0 g/l in water at 25° C.
 2. The phosphoric ester preparations according to claim 1 in which the oligomer mixture a) comprises at least three poly(alkylene phosphates) of the formula (I), in which R¹, R², R³ and R⁴ are respectively mutually independently a straight-chain or branched C₁- to C₄-alkyl moiety or a C₁- or C₂-alkoxyethyl moiety, A is a straight-chain or branched C₄- to C₁₀-alkylene moiety, or A is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C'CH₂—, a moiety of the formula —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, a moiety of the formula —CHR⁵—CHR⁶—S(O)_(b)—CHR⁷—CHR⁸— or a moiety of the formula —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—, in which a is an integer from 1 to 5, b is an integer from 0 to 2, c and d are mutually independently an integer from 1 to 5, R⁵, R⁶, R⁷ and R⁸ are mutually independently H or methyl, R⁹ is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C—CH₂—, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II)

a moiety of the formula (III)

a moiety of the formula (IV)

or a moiety of the formula —C(O)—R¹²—C(═O)—, where R¹⁰ and R¹¹ are respectively mutually independently H or C₁- or C₂-alkyl, R¹² is a straight-chain or branched C₂- to C₆-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a 1,4-phenylene moiety, and n is an integer from 0 to
 100. 3. The phosphoric ester preparations according to claim 1 in which the oligomer mixture a) comprises at least three poly(alkylene phosphates) of the formula (I) in which R¹, R², R³ and R⁴ are respectively mutually independently a straight-chain or branched C₁- to C₄-alkyl moiety or an n-butoxyethyl moiety, A is a straight-chain C₄- to C₆-alkylene moiety, or A is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C—CH₂—, a moiety of the formula —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, a moiety of the formula —CHR⁵—CHR⁶—S(O)_(b)—CHR⁷—CHR⁸— or a moiety of the formula —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—, in which a is an integer from 1 to 5, b is an integer from 0 to 2, c and d are mutually independently an integer from 1 to 5, R⁵, R⁶, R⁷ and R⁸ are mutually independently H or methyl, R⁹ is a moiety of the formula —CH₂—CH═CH—CH₂—, a moiety of the formula —CH₂—C≡C—CH₂—, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety, or a moiety of the formula (II)

a moiety of the formula (III)

a moiety of the formula (IV)

or a moiety of the formula —C(═O)—R¹²—C(═O)—, where R¹⁰ and R¹¹ are respectively mutually independently H or C₁- or C₂-alkyl, R¹² is a straight-chain or branched C₂- to C₆-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, or a 1,4-phenylene moiety, and n is an integer from 0 to
 100. 4. The phosphoric ester preparations according to claim 1 in which the oligomer mixture a) comprises at least three poly(alkylene phosphates) of the formula (I) in which R¹, R², R³ and R⁴ are identical and are ethyl, n-propyl, isopropyl, n-butyl, isobutyl or n-butoxyethyl, A is a straight-chain C₄- to C₆-alkylene moiety, or A is a moiety of the formulae

A is a moiety —CHR⁵—CHR⁶—(O—CHR⁷—CHR⁸)_(a)—, in which a is an integer from 1 to 2 and R⁵, R⁶, R⁷ and R⁸ are identical and are H, or is a moiety —(CHR⁵—CHR⁶—O)_(c)—R⁹—(O—CHR⁷—CHR⁸)_(d)—, in which c and d are mutually independently an integer from 1 to 2, R⁵, R⁶, R⁷ and R⁸ are identical and are H, R⁹ is a moiety of the formula (II), where R¹⁰ and R¹¹ are identical and are methyl, and n is an integer from 0 to
 20. 5. The phosphoric ester preparations according to claim 1 in which the phosphoric esters b) correspond to the formula (VIII)

in which R¹³, R¹⁴, R¹⁵ and R¹⁶ are respectively mutually independently straight-chain or branched C₄- to C₁₂-alkyl, C₄- to C₁₂-alkoxyalkyl, C₃- to C₁₂-chloroalkyl, C₃- to C₁₂-dichloroalkyl or optionally mono- or poly-C₁- to C₄-alkyl-substituted C₆- to C₁₀-aryl, X is a C₄- to C₈-alkylene moiety, a 1,2-phenylene moiety, a 1,3-phenylene moiety, a 1,4-phenylene moiety or a moiety of the formula (II),

in which R¹⁰ and R¹¹ are defined as in claim 1, and m is 0 or
 1. 6. The phosphoric ester preparations according to claim 1 in which the phosphoric esters b) are selected from the group of triphenyl phosphate, diphenyl cresyl phosphate, tricresyl phosphate, isopropylated or butylated aryl phosphates, bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), hydroquinone bis(diphenyl phosphate), neopentyl glycol bis(d(phenyl phosphate), triisobutyl phosphate, tributoxyethyl phosphate, tris(chloroisopropyl)phosphate and tris(dichloropropyl)phosphate.
 7. The phosphoric ester preparation according to claim 1 in which the materials are liquids with dynamic viscosity from 20 to 5000 mPas at 23° C.
 8. The phosphoric ester preparation according to claim 1 in which comprises from 30 to 70% by weight, preferably from 40 to 60% by weight, of the oligomer mixture a) and from 30 to 70% by weight, preferably from 40 to 60% by weight, of at least one phosphoric ester b), based on the entire preparation.
 9. The phosphoric ester preparation according to claim 1 in which comprises one or more auxiliaries selected from the group of the solvents, antioxidants, stabilizers and colorants.
 10. A process for the production of the phosphoric ester preparation according to claim 1 in which in oligomer mixture a) according to claim 1 and at least one phosphoric ester b) according to claim 1 are mixed with one another optionally in the presence of one or more auxiliaries.
 11. The use of the phosphoric ester preparation according to claim 1 as flame retardant.
 12. The use according to claim 11 in which the phosphoric ester preparation is used as flame retardant for polyurethanes.
 13. The use according to claim 12 in which the polyurethanes are foams, preferably flexible polyurethane foams based on polyether polyols or on polyester polyols.
 14. A flame retardant preparation comprising at least one phosphoric ester preparation according to claim 1, one or more flame retardants different from the phosphoric ester preparation and optionally one or more auxiliaries.
 15. A polyurethane comprising a phosphoric ester preparation according to at least one of claim
 1. 16. A polyurethane foam, preferably a flexible polyurethane foams based on polyether polyols or on polyester polyols, comprising a phosphoric ester preparation according to claim
 1. 17. A process for the production of a polyurethane according to claim 15 in which organic polyisocyanates are reacted, in the presence of a phosphoric ester composition according to at least one of claim 1 and in the presence of conventional blowing agents, stabilizers, activators and/or other conventional auxiliaries and additives, at a temperature from 20 to 80° C., with compounds having at least 2 hydrogen atoms reactive towards isocyanates.
 18. The process according to claim 17 in which the quantity used of the phosphoric ester preparation is from 0.5 to 30 parts by weight, preferably from 3 to 25 parts by weight, based on 100 parts by weight of polyol component.
 19. The use of the polyurethanes according to claim 15 in furniture cushioning, textile inlays, mattresses, vehicle seats, armrests, components, seat cladding and dashboard cladding, cable sheathing, gaskets, coatings, lacquers, adhesives, adhesion promoters and fibres.
 20. A hydraulic fluid comprising a phosphoric ester preparation according to claim
 1. 21. A process for reducing the hygroscopicity of poly(alkylene phosphates i) in which the poly(alkylene phosphate) is combined with from 40 to 230% by weight, based on the mass of the poly(alkylene phosphate), at least one phosphoric ester with solubility of less than 3.0 g/l in water at 25° C., and the mixture is homogenized.
 22. The process according to claim 21 in which the poly(alkylene phosphates) are an oligomer mixture a) according to claim
 1. 